THE ENVIRONMENTAL TECHNOLOGY VERIFICATION
PROGRAM
U.S. Environmental Protection Agency
Batreiie
Trtc Business o/ Innovation
ETV Joint Verification Statement
TECHNOLOGY TYPE: Dioxin Emission Monitoring System
APPLICATION: Monitoring Incinerator Emissions
TECHNOLOGY
NAME:
COMPANY:
ADDRESS:
WEB SITE:
E-MAIL:
Jet-REMPI
SRI International
333 Ravenswood Avenue PHONE: 650-859-3311
Menlo Park, CA 94025 FAX: 650-859-6196
www.sri.com
harald.oser^sri.com
The U.S. Environmental Protection Agency (EPA) has established the Environmental Technology Verification
(ETV) Program to facilitate the deployment of innovative or improved environmental technologies through
performance verification and dissemination of information. The goal of the ETV Program is to further
environmental protection by accelerating the acceptance and use of improved and cost-effective technologies.
ETV seeks to achieve this goal by providing high-quality, peer-reviewed data on technology performance to
those involved in the design, distribution, financing, permitting, purchase, and use of environmental
technologies. Information and ETV documents are available at www.epa.gov/etv.
ETV works in partnership with recognized standards and testing organizations, with stakeholder groups
(consisting of buyers, vendor organizations, and permitters), and with individual technology developers. The
program evaluates the performance of innovative technologies by developing test plans that are responsive to
the needs of stakeholders, conducting field or laboratory tests (as appropriate), collecting and analyzing data,
and preparing peer-reviewed reports. All evaluations are conducted in accordance with rigorous quality
assurance (QA) protocols to ensure that data of known and adequate quality are generated and that the results
are defensible.
The Advanced Monitoring Systems (AMS) Center, one of six technology areas under ETV, is operated by
Battelle in cooperation with EPA's National Exposure Research Laboratory. The AMS Center evaluated the
performance of the SRI Jet-REMPI (resonance enhanced multi-photon ionization) in monitoring emissions
of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). This verification
statement provides a summary of the test results.
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VERIFICATION TEST DESCRIPTION
The performance of the Jet-REMPI was evaluated in terms of relative accuracy (RA), range, data
completeness, and operational factors (ease of use, maintenance, and consumables/waste generated). RA and
range were determined by comparing Jet-REMPI results to those from reference samples collected
simultaneously using Method 23 sampling trains. Range was determined from measurements over a variety of
defined operating conditions that produced differing levels of PCDD/PCDFs. Data completeness was assessed
as the percentage of maximum data return achieved by the Jet-REMPI over the test period. Operational
factors were evaluated by means of operator observations and records of needed maintenance, vendor
activities, and expendables used.
A 2.94 thousand British thermal unit per hour, 3-Pass Wetback Scotch Marine Package Boiler (SMPB),
manufactured by Superior Boiler Works, Inc., and located at the EPA Research Triangle Park facility, was
used for the verification test. During this verification test, the SMPB was fully instrumented with continuous
emission monitors for a variety of species including oxygen, carbon monoxide, carbon dioxide, water, and
hydrogen chloride. Reference samples were collected and analyzed for PCDD/PCDFs using Method 23 with
several documented modifications.
QA oversight of verification testing was provided by Battelle and EPA. Battelle QA staff conducted a
technical systems audit, a performance evaluation audit, and a data quality audit of 10% of the test data.
This verification statement, the full report on which it is based, and the test/QA plan for this verification test
are all available atwww.epa.gov/etv/centers/centerl.html.
TECHNOLOGY DESCRIPTION
The following description of the Jet-REMPI is based on information provided by the vendor. This technology
description was not verified in this test.
Jet-REMPI is an analytical technique that is designed to selectively identify and quantify vapor-phase
constituents present at part-per-trillion levels in incinerator emissions without preconcentration or sample
collection. Ions produced by REMPI are typically detected using a time-of-flight mass spectrometer (TOP-
MS) that takes advantage of the pulsed nature and well-defined temporal character of laser ionization.
Simultaneous detection by mass and wavelength yields the extremely high chemical selectivity crucial to
identifying one trace compound in the midst of many other similar ones.
The laser system used in the verification test consists of a Nd:YAG pumped OPOTEK Vibrant OPO with
frequency doubling unit with a nominal tuning range between 250 and 340 nanometers, a 5-nanosecond pulse
width, and a repetition rate of 10 hertz. The optical line width of the system is approximately 2 centimeters
(cm)"1. The pulsed valve is an unmodified General Valve Series 9 unit, with an orifice diameter of
0.5 millimeter. The nominal opening time was 150 microseconds, with a 2.5-cm separation between the exit
of the valve and the ionization region. With the sample reservoir at atmospheric pressure, the two 250-liters-
per-second turbomolecular pumps (Varian Turbo V-250) maintain pressures in the ionization chamber and
mass spectrometer regions of 10"5 Torr, and 5 x 10"7 Torr, respectively. The mass spectrometric capabilities of
the reflectron-type TOP mass analyzer used in this verification test include an upper mass range typically up
to 500 atomic mass units and mass resolution (m/Am) greater than 500.
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VERIFICATION RESULTS
Parameter Evaluated
Relative accuracy
Range
Data completeness
Ease of use
Maintenance
Consumables/waste
generated
Method of Evaluation
Comparison to Method 23
reference samples
Comparison to Method 23
reference samples
Ratio of number of samples
successfully collected to
number of potential samples
that could have been
collected
Operator observations
Verification test staff
observations
Results
RA 78.2%
Intermethod RSD 61.5%
Intramethod RSD 8.4%
• Apparent dependence of accuracy on PCDD/F
toxic equivalent (TEQ) over range of
approximately 1 to 6 nanograms TEQ/dry standard
cubic meters with better agreement at high
concentration
• Apparent dependence of accuracy on sample
duration over range of 4 to 8 hours with better
agreement for longer sampling duration
• 100% completeness in number of samples collected
• Approximately 7% downtime
• Time required for installation of the Jet-REMPI
system was not verified
• Significant on-site support was needed during
testing. During routine operation, a representative
of ARCADIS was on-site and constantly
monitoring instrument diagnostic and indicator
signal
• Extensive training and experience with advanced
knowledge of mass spectrometry and laser
spectroscopy techniques is required for operation
of the Jet-REMPI and interpretation of the results
Repair of a faulty pulsed valve on a parallel Jet-REMPI
unit was required during the verification test. The
maintenance activities resulted in approximately
4 hours of instrument downtime.
Small amounts of compressed gas and calibration gas
standards were used during the verification test.
RSD = relative standard deviation
Original signed by Gregory A. Mack 6/6/06
Gregory A. Mack Date
Vice President
Energy, Transportation, and Environment Division
Battelle
Original signed by Lawrence W. Reiter
Lawrence W. Reiter
Director
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
7/26/06
Date
NOTICE: ETV verifications are based on an evaluation of technology performance under specific,
predetermined criteria and the appropriate quality assurance procedures. EPA and Battelle make no expressed or
implied warranties as to the performance of the technology and do not certify that a technology will always
operate as verified. The end user is solely responsible for complying with any and all applicable federal, state,
and local requirements. Mention of commercial product names does not imply endorsement.
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